Esters of trihalogentertiary butyl alcohol and process of forming same



lgliiSEZ Patented Jan. 30, 1923.

lJllE'lEffi STATES E A TENT FFECE.

THOIYLAS B. ALDRICH, O1 DETROIT, I1'IIGHIGAN, ASSIGNOR T0 PARKE, DAVIS &COMPANY, OF DETROIT, MCHIGA'N, A CORPORATION OF MICHIGAN.

ESTEES 0F TEIHALOGENTEETIARY BUT'YL ALCOHOL AND PROCESS OF FORMING-SAME.

I-l'o Drawing. Application filed May 18, 1918. Serial No. 285,343.

i'L-I m7 rZ'IIGHI, it may con-cam: formed a number of specific bodieshelon lie it known that I, fl-roams B. Amman, ing to this series,dilfering in the specific a citizen oil the United States of America,halogen used and also in the specific substiri-sidiug at Detroit, in thecounty of W'ayne tutions in the henzoyl group. As repremui State ofMichigan, have invented cersentativc of these I shall describe one ofthe lain new and useful Improvements in Esters scrics,-\ .iz the benzoicacid ester of tri' o'l lrihaiugi-uti-rtiary Butyl Alcohol andchlorotertiary-butyl-alcohol, which may lll Processes of Forming theSome, of which formed as follows: llie following is a specification.

The invention relates to a new series of: hol (suitably dehydrated) isheated on a bodies which may be designated as esters of steam bath withone part of benzoyl chloride triha-logentertiary-butyLalcohols, and thefor several hours, or until hydrochloric acid c-luu-acteristic featureof the series is th gas ceases to be given off, the reaction beingcombination of a benzoyl group with ages follows:trihalogentertiary-butyl-alcohol. I have l +HCI GE The reaction will bepractically ended in tyl-alcohol may be graphically represented sixhours. although there 1s no ob ect1on to as follows? heating for alonger period. As soon as completed, water is added and the ester thrownout in the form of an oil which solid- 01' 011 01! ifies on coolin Whilecooling it is best to n agitate the contents of the flash to prevent theester from forming a hard cake which is CH difficult to remove. When theester has solidified, the supernatant. liquid is decanted as and has thefollowing characteristics: It is {tinsel} as possible, an excess ofcaustic soda in the form of white crystals (mouorlinic) solution(iii-1095,.) is added, and the vessel having, a melting poini of 34 to35 heated. on the steam bath for about half an may he distilled underreduced pressure hour. By this procedure any of the triwithoutdecomposition, is readily soluble in chlorotertiary-butyl-alcohol orbenzoyl chlo organic solvents and practically insoluble ride remainingwill be decomposed or renin water, is not readily saponified. butboilrlered soluble in water. At the end of this ing with alkali (causticsoda 10%) decomtime. the flask is cooled as before and its conposes theester gradually, does not decomtents poured into a mortar and ground toa pose by boiling with concentrated nitric line powder. It is thenplaced on a suction acid, is not volatile in air but is slightlyvolfilter and washed a number of times with atile. with steam. coldwater. The substance thus obtained A. second specific body, benzoic acidester may be purified by recrystallization from a. oftribromotertiary-butyl-alcohol, is formed solvent, such as moderatelystrong alcohol. in a similar manner by the treatment of tri- Benzoicacid ester of trichlorotertiary-buhromotertiary-butyl-alcohol withbenzoyl One part of trichlorotcrtiary-butyl-alcochloride. Other specificbodies are the nitro benzoic esters of trihi1logentertiary-butyleilcohols-such for instance as the nitro benzoic ester oftribromotertiary-buty1-alcohol and the nitro benzoic ester oftrichlorotertiary-butyl-alcohol. Another process which CH CH CH on,cce-iion+nooc c AH. CH

solvents.

3. i-i new body forming one of a series which may be designated asesters of trichlorotertiarybntyl-alcohol and characterized by thecombination with trichlorotcrtiaryhntyl-alcohol of an acyl benzoylgroup, said body having the following characteristics:

may be used in the forming of bodies as above described is one involvingthe treatment of trihalogentertiary-butyl-alcoho1 and benzoic acid witha suitable condensing agent, such as zinc chloride, the reaction be ingas follows:

relative stability, iusolubility in water and extreme solubility in theorganic solvents.

'3. The newbody, benzoic acid ester of trichlorotertiary-butyl-alcoholhaving the fol lowing characteristics: in the form of white crystalshaving a melting point of 34 to 35 C., may be distilled underreducedpressure without decomposition, is readily solublc in organicsolvents and practically insoluble in water, is not readily saponificd,will be decomposed gradually on boiling with alkali, does not decomposeby boiling with concentrated nitric acid, is not volatile in Water butis slightly volatile with steam.

In testimony whereof I affix my signature.

THOMAS B. ALDRICH.

